On‐Chip Chemical Self‐Assembly of Semiconducting Single‐Walled Carbon Nanotubes (SWNTs): Toward Robust and Scale Invariant SWNTs Transistors

In this paper, the fabrication of carbon nanotubes field effect transistors by chemical self‐assembly of semiconducting single walled carbon nanotubes (s‐SWNTs) on prepatterned substrates is demonstrated. Polyfluorenes derivatives have been demonstrated to be effective in selecting s‐SWNTs from raw mixtures. In this work the authors functionalized the polymer with side chains containing thiols, to obtain chemical self‐assembly of the selected s‐SWNTs on substrates with prepatterned gold electrodes. The authors show that the full side functionalization of the conjugated polymer with thiol groups partially disrupts the s‐SWNTs selection, with the presence of metallic tubes in the dispersion. However, the authors determine that the selectivity can be recovered either by tuning the number of thiol groups in the polymer, or by modulating the polymer/SWNTs proportions. As demonstrated by optical and electrical measurements, the polymer containing 2.5% of thiol groups gives the best s‐SWNT purity. Field‐effect transistors with various channel lengths, using networks of SWNTs and individual tubes, are fabricated by direct chemical self‐assembly of the SWNTs/thiolated‐polyfluorenes on substrates with lithographically defined electrodes. The network devices show superior performance (mobility up to 24 cm² V^?1 s^?1), while SWNTs devices based on individual tubes show an unprecedented (100%) yield for working devices. Importantly, the SWNTs assembled by mean of the thiol groups are stably anchored to the substrate and are resistant to external perturbation as sonication in organic solvents.     

Electronic‐Type‐ and Diameter‐Dependent Reduction of Single‐Walled Carbon Nanotubes Induced by Adsorption of Electron‐Donor Molecules

The adsorption of the organic donor molecules tetrakis(dimethylamino)ethylene (TDAE) and cobaltocene (CoCp₂) on high‐pressure CO decomposition (HiPco) single‐walled carbon nanotubes (SWNTs) is investigated using density functional theory (DFT), optical absorption, and Raman spectra methods. The selective reduction of SWNTs according to the electronic type and diameter of SWNTs is revealed. The reduction rate decreases in the order: metallic SWNTs ≥ large‐diameter semiconducting SWNTs > small‐diameter semiconducting SWNTs.     

Wafer‐Scale Fabrication of Suspended Single‐Walled Carbon Nanotube Arrays by Silver Liquid Dynamics

Suspended single‐walled carbon nanotubes (SWNTs) have advantages in mechanical resonators and highly sensitive sensors. Large‐scale fabrication of suspended SWNTs array devices and uniformity among SWNTs devices remain a great challenge. This study demonstrates an effective, fast, and wafer‐scale technique to fabricate suspended SWNT arrays, which is based on a dynamic motion of silver liquid to suspend and align the SWNTs between the prefabricated palladium electrodes in high temperature annealing treatment. Suspended, strained, and aligned SWNTs are synthesized on a 2 × 2 cm² substrate with an average density of 10 tubes per micrometer. Under the optimal conditions, almost all SWNTs become suspended. A promising formation model of suspended SWNTs is established. The Kelvin four‐terminal resistance measurement shows that these SWNT array devices have extreme low contact resistance. Meanwhile, the suspended SWNT array field effect transistors are fabricated by selective etching of metallic SWNTs using electrical breakdown. This method of large‐scale fabrication of suspended architectures pushes the study of nanoscale materials into a new stage related to the electrical physics and industrial applications.     

High‐Performance Partially Aligned Semiconductive Single‐Walled Carbon Nanotube Transistors Achieved with a Parallel Technique

Single‐walled carbon nanotubes (SWNTs) are widely thought to be a strong contender for next‐generation printed electronic transistor materials. However, large‐scale solution‐based parallel assembly of SWNTs to obtain high‐performance transistor devices is challenging. SWNTs have anisotropic properties and, although partial alignment of the nanotubes has been theoretically predicted to achieve optimum transistor device performance, thus far no parallel solution‐based technique can achieve this. Herein a novel solution‐based technique, the immersion‐cum‐shake method, is reported to achieve partially aligned SWNT networks using semiconductive (99% enriched) SWNTs (s‐SWNTs). By immersing an aminosilane‐treated wafer into a solution of nanotubes placed on a rotary shaker, the repetitive flow of the nanotube solution over the wafer surface during the deposition process orients the nanotubes toward the fluid flow direction. By adjusting the nanotube concentration in the solution, the nanotube density of the partially aligned network can be controlled; linear densities ranging from 5 to 45 SWNTs/μm are observed. Through control of the linear SWNT density and channel length, the optimum SWNT‐based field‐effect transistor devices achieve outstanding performance metrics (with an on/off ratio of ~3.2 × 10⁴ and mobility 46.5 cm²/Vs). Atomic force microscopy shows that the partial alignment is uniform over an area of 20 × 20 mm² and confirms that the orientation of the nanotubes is mostly along the fluid flow direction, with a narrow orientation scatter characterized by a full width at half maximum (FWHM) of <15° for all but the densest film, which is 35°. This parallel process is large‐scale applicable and exploits the anisotropic properties of the SWNTs, presenting a viable path forward for industrial adoption of SWNTs in printed, flexible, and large‐area electronics.     

Short channel field-effect transistors from highly enriched semiconducting carbon nanotubes

Semiconducting single-walled carbon nanotubes (s-SWNTs) with a purity of ∼98% have been obtained by gel filtration of arc-discharge grown SWNTs with diameters in the range 1.2–1.6 nm. Multi-laser Raman spectroscopy confirmed the presence of less than 2% of metallic SWNTs (m-SWNTs) in the s-SWNT enriched sample. Measurement of ∼50 individual tubes in Pd-contacted devices with channel length 200 nm showed on/off ratios of >10⁴, conductances of 1.38–5.8 μS, and mobilities in the range 40–150 cm²·V/s. Short channel multi-tube devices with ∼100 tubes showed lower on/off ratios due to residual m-SWNTs, although the on-current was greatly increased relative to the devices made from individual tubes.      

Diameter‐ and Metallicity‐Selective Enrichment of Single‐Walled Carbon Nanotubes Using Polymethacrylates with Pendant Aromatic Functional Groups

Current methods for the synthesis of single‐walled nanotubes (SWNTs) produce mixtures of semiconducting (sem‐) and metallic (met‐) nanotubes. Most approaches to the chemical separation of sem‐/met‐SWNTs are based on small neutral molecules or conjugated aromatic polymers, which characteristically have low separation/dispersion efficiencies or present difficulties in the postseparation removal of the polymer so that the resulting field‐effect transistors (FETs) have poor performance. In this Full Paper, the use of three polymethacrylates with different pendant aromatic functional groups to separate cobalt–molybdenum catalyst (CoMoCAT) SWNTs according to their metallicity and diameters is reported. UV/Vis/NIR spectroscopy indicates that poly(methyl‐methacrylate‐co‐fluorescein‐o‐acrylate) (PMMAFA) and poly(9‐anthracenylmethyl‐methacrylate) (PAMMA) preferentially disperse semiconducting SWNTs while poly(2‐naphthylmethacrylate) (PNMA) preferentially disperses metallic SWNTs, all in dimethylforamide (DMF). Photoluminescence excitation (PLE) spectroscopy indicates that all three polymers preferentially disperse smaller‐diameter SWNTs, particularly those of (6,5) chirality, in DMF. When chloroform is used instead of DMF, the larger‐diameter SWNTs (8,4) and (7,6) are instead selected by PNMA. The solvent effects suggest that diameter selectivity and change of polymer conformation is probably responsible. Change of the polymer fluorescence upon interaction with SWNTs indicates that metallicity selectivity presumably results from the photon‐induced dipole–dipole interaction between polymeric chromophore and SWNTs. Thin‐film FET devices using semiconductor‐enriched solution with PMMAFA have been successfully fabricated and the device performance confirms the sem‐SWNTs enrichment with a highly reproducible on/off ratio of about 10³.     

High yield spray forming of small diameter tubes using pressure‐gas‐atomization

The economy of the spray forming process is restricted by the generation of overspray, which in many cases cannot be re‐introduced into the process by re‐melting or co‐injection. Especially for small deposits, such as small diameter tubes (diameter <100 mm), the amount of overspray can become large in conventional spray‐forming processes. In this work, an alternative process with a pressure‐gas‐atomizer operating at low melt flows is presented. Tubes with diameters of 50 mm and 90 mm were spray‐formed and analyzed regarding yield and porosity. It was found that yields up to 96% can be achieved with porosities below 1% if proper process parameters are identified and used. An evaluation of the yield and the corresponding achievable porosity is conducted to identify resource‐efficient sets of parameters.     

Photon‐Pair Generation with a 100 nm Thick Carbon Nanotube Film

Nonlinear optics based on bulk materials is the current technique of choice for quantum‐state generation and information processing. Scaling of nonlinear optical quantum devices is of significant interest to enable quantum devices with high performance. However, it is challenging to scale the nonlinear optical devices down to the nanoscale dimension due to relatively small nonlinear optical response of traditional bulk materials. Here, correlated photon pairs are generated in the nanometer scale using a nonlinear optical device for the first time. The approach uses spontaneous four‐wave mixing in a carbon nanotube film with extremely large Kerr‐nonlinearity (≈100 000 times larger than that of the widely used silica), which is achieved through careful control of the tube diameter during the carbon nanotube growth. Photon pairs with a coincidence to accidental ratio of 18 at the telecom wavelength of 1.5 µm are generated at room temperature in a ≈100 nm thick carbon nanotube film device, i.e., 1000 times thinner than the smallest existing devices. These results are promising for future integrated nonlinear quantum devices (e.g., quantum emission and processing devices).     

Growth of Single‐Walled Carbon Nanotubes with Different Chirality on Same Solid Cobalt Catalysts at Low Temperature

Currently, designing solid catalysts at high temperature is the main strategy to realize single‐walled carbon nanotubes (SWNTs) with specific chirality, meaning it is very hard and challenging to create new catalysts or faces to fit new chirality. However, low temperatures make most catalysts solid, and developing solid catalysts at low temperature is desired to realize chirality control of SWNTs. A rational approach to grow SWNTs array with different chiralities on same solid Co catalysts at low temperature (650 °C) is herein put forward. Using solid Co catalysts, near‐armchair (10, 9) tubes horizontal array with ≈75% selectivity and (12, 6) tubes array with ≈82% are realized by adopting a small amount of ethanol and large amount of CO respectively. (10, 9) tubes are enriched for thermodynamic stability and (12, 6) tubes for kinetics growth rate. Both kinds of tubes show a similar symmetry to the Co (1 1 1) face with threefold symmetry for the symmetry matching nucleation mechanism proposed earlier. This method provides a new strategy to study the nucleation mechanism and more possibilities for preparing new solid catalysts to control the structure of SWNTs.     

Raman-active modes of single-walled carbon nanotubes derived from the gas-phase decomposition of CO (HiPco process)

Here we report Raman scattering studies of ropes of Single-walled carbon nanotubes (SWNTs) grown by a high CO pressure process. Five samples from five different batches were studied as a function of excitation wavelength. Three of these samples exhibited Raman spectra similar to that found for SWNTs made by pulsed laser vaporization of arc-discharge methods. The other two samples were found by Raman scattering to contain a significant fraction of tubes with diameter < 1.0 nm. These samples exhibited unusual spectra that, however, can be well understood within the existing models for the electronic and phononic states in SWNTs. Spectra recorded with 1064 nm for the sample having a significant fraction of smaller diameter tubes shows strong modes present between 500 and 1200 cm-1. We suggest these modes arise due to the enhancement of Raman cross-section for small diameter tubes.     

Efficient Near‐Infrared Electroluminescence at 840 nm with “Metal‐Free” Small‐Molecule:Polymer Blends

Due to the so‐called energy‐gap law and aggregation quenching, the efficiency of organic light‐emitting diodes (OLEDs) emitting above 800 nm is significantly lower than that of visible ones. Successful exploitation of triplet emission in phosphorescent materials containing heavy metals has been reported, with OLEDs achieving remarkable external quantum efficiencies (EQEs) up to 3.8% (peak wavelength > 800 nm). For OLEDs incorporating fluorescent materials free from heavy or toxic metals, however, we are not aware of any report of EQEs over 1% (again for emission peaking at wavelengths > 800 nm), even for devices leveraging thermally activated delayed fluorescence (TADF). Here, the development of polymer light‐emitting diodes (PLEDs) peaking at 840 nm and exhibiting unprecedented EQEs (in excess of 1.15%) and turn‐on voltages as low as 1.7 V is reported. These incorporate a novel triazolobenzothiadiazole‐based emitter and a novel indacenodithiophene‐based transport polymer matrix, affording excellent spectral and transport properties. To the best of knowledge, such values are the best ever reported for electroluminescence at 840 nm with a purely organic and solution‐processed active layer, not leveraging triplet‐assisted emission.     

Self‐Sorting of 10‐µm‐Long Single‐Walled Carbon Nanotubes in Aqueous Solution

Single‐walled carbon nanotubes (SWCNTs) are a class of 1D nanomaterials that exhibit extraordinary electrical and optical properties. However, many of their fundamental studies and practical applications are stymied by sample polydispersity. SWCNTs are synthesized in bulk with broad structural (chirality) and geometrical (length and diameter) distributions; problematically, all known post‐synthetic sorting methods rely on ultrasonication, which cuts SWCNTs into short segments (typically <1 µm). It is demonstrated that ultralong (>10 µm) SWCNTs can be efficiently separated from shorter ones through a solution‐phase “self‐sorting”. It is shown that thin‐film transistors fabricated from long semiconducting SWCNTs exhibit a carrier mobility as high as ≈90 cm² V^?1 s^?1, which is ≈10 times higher than those which use shorter counterparts and well exceeds other known materials such as organic semiconducting polymers (<1 cm² V^?1 s^?1), amorphous silicon (≈1 cm² V^?1 s^?1), and nanocrystalline silicon (≈50 cm² V^?1 s^?1). Mechanistic studies suggest that this self‐sorting is driven by the length‐dependent solution phase behavior of rigid rods. This length sorting technique shows a path to attain long‐sought ultralong, electronically pure carbon nanotube materials through scalable solution processing.     

Ultrathin and Stretchable Rechargeable Devices with Organic Polymer Nanosheets Conformable to Skin Surface

Ultrathin flexible electronic devices have been attracting substantial attention for biomonitoring, display, wireless communication, and many other ubiquitous applications. In this article, organic robust redox‐active polymer/carbon nanotube hybrid nanosheets with thickness of just 100 nm are reported as power sources for ultrathin devices conformable to skin. Regardless of the extreme thinness of the electrodes, a moderately large current density of 0.4 mA cm^?2 is achieved due to the high output of the polymers (>10 A g^?1). For the first time, the use of mechanically robust yet intrinsically soft electrodes and polymer nanosheet sealing leads to the fabrication of rechargeable devices with only 1‐µm thickness and even with stretchable properties.     

Solution‐Processed All‐Ceramic Plasmonic Metamaterials for Efficient Solar–Thermal Conversion over 100–727 °C

Low‐cost and large‐area solar–thermal absorbers with superior spectral selectivity and excellent thermal stability are vital for efficient and large‐scale solar–thermal conversion applications, such as space heating, desalination, ice mitigation, photothermal catalysis, and concentrating solar power. Few state‐of‐the‐art selective absorbers are qualified for both low‐ ( < 200  ° C) and high‐temperature ( > 600  ° C) applications due to insufficient spectral selectivity or thermal stability over a wide temperature range. Here, a high‐performance plasmonic metamaterial selective absorber is developed by facile solution‐based processes via assembling an ultrathin ( ≈ 120 nm) titanium nitride (TiN) nanoparticle film on a TiN mirror. Enabled by the synergetic in‐plane plasmon and out‐of‐plane Fabry–Pérot resonances, the all‐ceramic plasmonic metamaterial simultaneously achieves high, full‐spectrum solar absorption (95%), low mid‐IR emission (3% at 100  ° C), and excellent stability over a temperature range of 100–727  ° C, even outperforming most vacuum‐deposited absorbers at their specific operating temperatures. The competitive performance of the solution‐processed absorber is accompanied by a significant cost reduction compared with vacuum‐deposited absorbers. All these merits render it a cost‐effective, universal solution to offering high efficiency (89–93%) for both low‐ and high‐temperature solar–thermal applications.     

Diameter and Density Control of Single‐Walled Carbon Nanotube Forests by Modulating Ostwald Ripening through Decoupling the Catalyst Formation and Growth Processes

A continuous and wide range control of the diameter (1.9?3.2 nm) and density (0.03?0.11 g cm^?3) of single‐walled carbon nanotube (SWNT) forests is demonstrated by decoupling the catalyst formation and SWNT growth processes. Specifically, by managing the catalyst formation temperature and H₂ exposure, the redistribution of the Fe catalyst thin film into nanoparticles is controlled while a fixed growth condition preserved the growth yield. The diameter and density are inversely correlated, where low/high density forests would consist of large/small diameter SWNTs, which is proposed as a general rule for the structural control of SWNT forests. The catalyst formation process is modeled by considering the competing processes, Ostwald ripening, and subsurface diffusion, where the dominant mechanism is found to be Ostwald ripening. Specifically, H₂ exposure increases catalyst surface energy and decreases diameter, while increased temperature leads to increased diffusion on the surface and an increase in diameter.     

Cancer‐Cell Targeting and Photoacoustic Therapy Using Carbon Nanotubes as “Bomb” Agents

A unique approach using the large photoacoustic effect of single‐walled carbon nanotubes (SWNTs) for targeting and selective destruction of cancer cells is demonstrated. SWNTs exhibit a large photoacoustic effect in suspension under the irradiation of a 1064‐nm Q‐switched millisecond pulsed laser and trigger a firecracker‐like explosion at the nanoscale. By using such an explosion, a photoacoustic agent is developed by functionalizing the SWNTs with folate acid (FA) that can selectively bind to cancer cells overexpressing folate receptor on the surface of the cell membrane and kill them through SWNT explosion inside the cells under the excitation of millisecond pulsed laser. The uptake pathway of folate‐conjugated SWNTs into cancer cells is investigated via fluorescence imaging and it is found that the FA‐SWNTs can enter into cancer cells selectively with a high targeting capability of 17–28. Under the treatment of 1064‐nm millisecond pulsed laser, 85% of cancer cells with SWNT uptake die within 20 s, while 90% of the normal cells remain alive due to the lack of SWNTs inside cells. Temperature changes during laser treatment are monitored and no temperature increases of more than ± 3 °C are observed. With this approach, the laser power used for cancer killing is reduced 150–1500 times and the therapy efficiency is improved. The death mechanism of cancer cells caused by the photoacoustic explosion of SWNTs is also studied and discussed in detail. These discoveries provide a new way to use the photoacoustic properties of SWNTs for therapeutic applications.     

Two‐Photon Vertical‐Flow Lithography for Microtube Synthesis

Two‐photon vertical‐flow lithography is demonstrated for synthesis of complex‐shaped polymeric microtubes with a high aspect ratio (>100:1). This unique microfluidic approach provides rigorous control over the morphology and surface topology to generate thin‐walled (<1 µm) microtubes with a tunable diameter (1–400 µm) and pore size (1–20 µm). The interplay between fluid‐flow control and two‐photon lithography presents a generic high‐resolution method that will substantially contribute toward the future development of biocompatible scaffolds, stents, needles, nerve guides, membranes, and beyond.     

Host–Guest Hybrid Redox Materials Self‐Assembled from Polyoxometalates and Single‐Walled Carbon Nanotubes

The development of next‐generation molecular‐electronic, electrocatalytic, and energy‐storage systems depends on the availability of robust materials in which molecular charge‐storage sites and conductive hosts are in intimate contact. It is shown here that electron transfer from single‐walled carbon nanotubes (SWNTs) to polyoxometalate (POM) clusters results in the spontaneous formation of host–guest POM@SWNT redox‐active hybrid materials. The SWNTs can conduct charge to and from the encapsulated guest molecules, allowing electrical access to >90% of the encapsulated redox species. Furthermore, the SWNT hosts provide a physical barrier, protecting the POMs from chemical degradation during charging/discharging and facilitating efficient electron transfer throughout the composite, even in electrolytes that usually destroy POMs.     

High‐Responsivity Photodetection by a Self‐Catalyzed Phase‐Pure p‐GaAs Nanowire

Defects are detrimental for optoelectronics devices, such as stacking faults can form carrier‐transportation barriers, and foreign impurities (Au) with deep‐energy levels can form carrier traps and nonradiative recombination centers. Here, self‐catalyzed p‐type GaAs nanowires (NWs) with a pure zinc blende (ZB) structure are first developed, and then a photodetector made from these NWs is fabricated. Due to the absence of stacking faults and suppression of large amount of defects with deep energy levels, the photodetector exhibits room‐temperature high photoresponsivity of 1.45 × 10⁵ A W^?1 and excellent specific detectivity (D*) up to 1.48 × 10¹⁴ Jones for a low‐intensity light signal of wavelength 632.8 nm, which outperforms previously reported NW‐based photodetectors. These results demonstrate these self‐catalyzed pure‐ZB GaAs NWs to be promising candidates for optoelectronics applications.     

Enrichment of (8,4) Single‐Walled Carbon Nanotubes Through Coextraction with Heparin

Heparin sodium salt is investigated as a dispersant for dispersing single‐walled carbon nanotubes (SWNTs). Photoluminescence excitation (PLE) spectroscopy is used for identification and abundance estimation of the chiral species. It is found that heparin sodium salt preferentially disperses larger‐diameter Hipco SWNTs. When used to disperse CoMoCAT nanotube samples, heparin has a strong preference for (8,4) tubes, which have larger diameter than the predominant (6,5) in pristine CoMoCAT samples. PLE intensity due to (8,4) tubes increases from 7% to 60% of the total after threefold extractions. Computer modeling verifies that the complex of (8,4) SWNTs and heparin has the lowest binding energy amongst the four semiconducting species present in CoMoCAT. Network field‐effect transistors are successfully made with CoMoCAT/heparin and CoMoCAT/sodium dodecylbenzene sulfonate (SDBS)–heparin (x3), confirming the easy removability of heparin.